For the first time, hollow-fiber liquid-phase microextraction combined with high-performance liquid chromatography-ultraviolet was used to extract trans,trans-muconic acid, in urine samples of workers who had been exposed to benzene. The parameters affecting the metabolite extraction were optimized as follows: the volume of sample solution was 11 mL with pH 2, liquid membrane containing dihexyl ether as the supporter, 15% (w/v) of trioctylphosphine oxide as the carrier, the time of extraction was 120 minutes, and stirring rate was 500 rpm. Organic phase impregnated in the pores of a hollow fiber was extracted into 24 µL solution of 0.05 mol L(-1) Na2CO3 located inside the lumen of the fiber. Under optimized conditions, a high enrichment factor of 153-182 folds, relative recovery of 83%-92%, and detection limit of 0.001 µg mL(-1) were obtained. The method was successfully applied to the analysis of ttMA in real urine samples.